Physics – Condensed Matter – Materials Science
Scientific paper
Mar 2001
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2001mms..conf..164d&link_type=abstract
Microgravity Materials Science Conference 2000, vol. 1, p. 164
Physics
Condensed Matter
Materials Science
Mars Surface, Supercritical Fluids, Extraction, Precipitates, Carbon Dioxide, Carbonyl Compounds, Tetrachlorides, Low Molecular Weights, Polarity, Solubility
Scientific paper
We are investigating the use of supercritical fluids to extract mineral and/or carbonaceous material from Martian surface soils and its igneous crust. Two candidate supercritical fluids are carbon dioxide and water. The Martian atmosphere is composed mostly of carbon dioxide (approx. 95.3%) and could therefore provide an in-situ source of carbon dioxide. Water, although present in the Martian atmosphere at only approx. 0.03%, is also a candidate supercritical solvent. Previous work done with supercritical fluids has focused primarily on their solvating properties with organic compounds. Interestingly, the first work reported by Hannay and Hogarth at a meeting of the Royal Society of London in 1879 observed that increasing or decreasing the pressure caused several inorganic salts e.g., cobalt chloride, potassium iodide, and potassium bromide, to dissolve or precipitate in supercritical ethanol. In high-pressure boilers, silica, present in most boiler feed waters, is dissolved in supercritical steam and transported as dissolved silica to the turbine blades. As the pressure is reduced the silica precipitates onto the turbine blades eventually requiring the shutdown of the generator. In supercritical water oxidation processes for waste treatment, dissolved salts present a similar problem. The solubility of silicon dioxide (SiO2) in supercritical water is shown. The solubility curve has a shape characteristic of supercritical systems. At a high pressure (greater than 1750 atmospheres) increasing the temperature results in an increase in solubility of silica, while at low pressures, less than 400 atm., the solubility decreases as temperature increases. There are only a few studies in the literature where supercritical fluids are used in extractive metallurgy. Bolt modified the Mond process in which supercritical carbon monoxide was used to produce nickel carbonyl (Ni(CO)4). Tolley and Tester studied the solubility of titanium tetrachloride (TiCl4) in supercritical CO2. They reported complete miscibility of TiCl4 with supercritical CO2 (infinite solubility). At 1500 psig, TiCl4 and CO2 form a single liquid phase below 50 C. Tolley et al. also reported on the solubility and thermodynamics of tin tetrachloride in supercritical CO2. Some of their data for TiC14 are shown. Three criteria have been suggested to predict which materials are suitable for supercritical extraction: 1) Hydrocarbons or lipophilic compounds of low molecular weight and polarity are easily extracted with supercritical CO2. 2) Compounds with polar groups are not easily extracted with supercritical CO2. 3) Separation of mixtures is facilitated if components differing mass, vapor pressure, or polarity.
Debelak Kenneth A.
Roth John A.
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